JP4877702B2 - Novel dye and colored photosensitive composition using the same - Google Patents

Description

The present invention relates to a dye suitable for production of a color filter used in a liquid crystal display element or a solid-state image sensor, a negative coloring photosensitive composition, a color filter, a liquid crystal display element having the same and a solid-state image sensor.

Colors of solid-state imaging devices such as liquid crystal display devices such as liquid crystal displays (LCD) typified by notebook computers and liquid crystal televisions, and charge coupled devices (CCD) used as input devices for digital cameras and color copiers Color filters are required for conversion. As a method for producing a color filter used in these liquid crystal display devices and solid-state imaging devices, there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and a dye internal addition method.

Among the various methods described above, in particular, smoothness, signal characteristics as a solid-state imaging device, and dye addition method that is excellent in terms of simplification of the manufacturing process, the characteristics required of the dye include good spectral characteristics, high solvent solubility, There are compatibility with resin components and anti-color loss characteristics during development. However, even when a commercially available dye is used, there are no pigments that satisfy all of the above characteristics, and it has been difficult to obtain a good colored photosensitive composition.

JP-A-1-168775 JP-A-4-110533

  Therefore, the present invention is to provide a coloring photosensitive composition dye having good spectral characteristics, high solvent solubility, compatibility with a resin component, and good color loss resistance during development.

  That is, the present invention has been made to solve the above problems, and the gist of the present invention is as follows.

〔式中Ｒ₁は、置換されていても良いその総炭素数が４以上２０以下のアルキル基、アルケニル基を表し、Ｒ₂は水素またはメチル基を表し、Ｘは水素原子またはアルカリ金属を表す。〕
で示される色素。
（２）Ｒ₁が炭素数４〜１０の直鎖状のアルキル基である請求項１に記載の色素。
（３）バインダーポリマー、光重合性モノマーまたはオリゴマー、熱硬化剤、光開始剤、染料、有機溶剤を含有する組成物であって、染料のすべて、または一部に一般式（I）で表される色素を使用することを特徴とするアルカリ現像型ネガ型着色感光性組成物。
（４）請求項２または３に記載のネガ型着色感光性組成物を用いて作成されたカラーフィルターを有する液晶表示素子。
（５）請求項２または３に記載のネガ型着色感光性組成物を用いて作成されたカラーフィルターを有する固体撮像素子。
で示される。 (1) General formula (I)

[Wherein R ₁ represents an optionally substituted alkyl group or alkenyl group having 4 to 20 carbon atoms in total, R ₂ represents hydrogen or a methyl group, and X represents a hydrogen atom or an alkali metal. . ]
Dye represented by
(2) The dye according to claim 1, wherein R ₁ is a linear alkyl group having 4 to 10 carbon atoms.
(3) A composition containing a binder polymer, a photopolymerizable monomer or oligomer, a thermosetting agent, a photoinitiator, a dye, and an organic solvent, all or part of the dye represented by the general formula (I) An alkali-developing negative coloring photosensitive composition characterized by using a dye.
(4) A liquid crystal display device having a color filter produced using the negative coloring photosensitive composition according to claim 2 or 3.
(5) A solid-state imaging device having a color filter produced using the negative coloring photosensitive composition according to claim 2 or 3.
Indicated by

By using the dye of the present invention, a colored photosensitive composition having good spectral characteristics, high solvent solubility, compatibility with resin components, and good color loss resistance during development can be obtained. In particular, in the present invention, R ₁ in the general formula (1) is preferably an alkyl group or an alkenyl group having a total number of carbons of 4 or more and 20 or less. The reason for this is that the solvent solubility of the dye obtained when the carbon number is less than 4 and the compatibility with the resin component are insufficient, and the color value per weight of the dye obtained when the carbon number is 21 or more. Is reduced, and the coloring power of the colored photosensitive composition using the same is greatly reduced.

In order to increase the solubility of the dye in an organic solvent, for example, an acid dye, a direct dye, a sulfone group of a reactive dye and a salt of an alkylamine are used. Examples of alkylamines include amine salts such as n-propylamine, 2-ethylhexyloxypropylamine, 2-ethylhexyloxypropylamine, and dibutylamine. When used in a development-type negative coloring photosensitive composition, the amine salt is dissociated by alkali, and the dye base is dissolved in the alkali developer. For this reason, there is a problem that the dye is removed from the pixel formed by the development, and it is difficult to obtain the target color density. In order to solve such a problem, in the present invention, an alkyl group or an alkenyl group is introduced as R _{1 in} the dye base to achieve solvent solubility, compatibility with a resin, and suppression of dissolution in an alkyl developer. Is.

In the general formula (1), examples of the alkyl group represented by R ₁ include a substituted or unsubstituted alkyl group. Examples of the unsubstituted alkyl group include a linear or branched alkyl group. Examples of the linear alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, C4 to C10 linear alkyl groups such as a decyl group are exemplified, and examples of the branched alkyl group include C4 to C10 branched chain groups such as isobutyl group, isopentyl group, isohexyl group, and 2-ethylhexyl group. And an alkyl group.

Examples of the substituted alkyl group include, but are not limited to, a hydroxy substituted alkyl group, a cyano substituted alkyl group, a halogen atom substituted alkyl group, an alkoxy substituted alkyl group, and an alkoxyalkoxy substituted alkyl group. Examples of the hydroxy-substituted alkyl group include 4-hydroxybutyl group, and examples of the cyano-substituted alkyl group include C4-C6 cyano-substituted alkyl groups such as 4-cyanobutyl group and 6-cyanohexyl. Examples of the substituted alkyl group include C4-C6 halogen atom-substituted alkyl groups such as 4-chlorobutyl group, 5-bromopentyl group, hexafluorobutyl group and the like.

Examples of the alkoxy-substituted alkyl group include 2-ethoxyethyl group, 2- (n) propoxyethyl group, 2- (iso) propoxyethyl group, 2- (n) butoxyethyl group, 2- (iso) butoxyethyl group, (C1-C8) alkoxy-substituted (C2-C4) alkyl groups such as 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 2-methoxypropyl group and the like, and alkoxyalkoxy Examples of the substituted alkyl group include 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2- (n) propoxyethoxy) ethyl group, 2- (2- (iso) ) Propoxyethoxy) ethyl group, 2- (2- (n) butoxyethoxy) ethyl group, 2- (2- (iso) butoxyethoxy) Ethyl group, 2- {2- (2-ethylhexyl oxy) ethoxy} and ethyl group (C1 to C8) alkoxy (C1 to C8) alkoxy-substituted (C2-C4) alkyl group.

Examples of the alkenyl group for R ₁ include straight-chain alkenyl groups such as a butenyl group, a hexenyl group, a pentenyl group, and an octenyl group.
Among these groups, preferred R ₁ is, for example, carbon number such as n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Examples thereof include 4 to 10 linear alkyl groups.

In the general formula (1), examples of R ₂ include a hydrogen atom or a methyl group, and a methyl group is preferable.
Examples of X in the general formula (1) include an alkali metal and a hydrogen atom.
Next, representative examples of the dye of the present invention are shown.

(Table 1)
Table 1
Compound No. R ₁ R ₂ X
1 n-butyl methyl H
2 n-butyl methyl Na
3 n-pentyl methyl H
4 n-pentyl methyl Na
5 n-heptyl methyl H
6 n-heptyl methyl Na
7 n-octyl methyl H
8 n-octyl methyl Na
9 n-butyl H H
10 n-Butyl H Na
11 n-pentyl H H
12 n-pentyl H Na
13 n-heptyl H H
14 n-heptyl H Na
15 n-octyl H H
16 n-octyl H Na
17 Ethoxyethyl methyl Na
18 n-butoxyethyl methyl H
19 Ethoxyethyl H Na
20 n-butoxyethyl H H
21 Cyano-n-butyl methyl Na
22 Cyano-n-butyl H H

The dye of the present invention can be obtained by alkylating or alkenylating an existing dye by a known method. Examples of the existing dye include CI Acid Blue 83 (R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, X is Na), and CI Acid Blue 90 (R ₁ is a hydrogen atom, R ₂ is a methyl group, and X is Na). The dye of the present invention can be obtained by alkylating or alkenylating the —NH— moiety in the existing dye structure. As a method of alkylation or alkenylation, a method of reacting an alkyl halide (alkene) with an alkali in a solvent, or a method of using an alkyl tosyl (alkenyl) ester and an alkali is common.

The alkylation is carried out in an organic solvent by stirring for several hours at a temperature of 50 to 130 ° C., more preferably 60 to 110 ° C. As the organic solvent, the above may be CI Acid Blue 83 and CI Acid Blue 90, which are soluble in alkyl halide and alkyl tosylate, and specific examples thereof include dimethylformamide, dimethylacetamide, N-methylpyrrolidone. , Sulfolane and the like, but are not limited thereto. The alkyl halide or alkyl tosylate and alkali described above are added to the solvent in an amount of 1 to 5 times mol, more preferably 1 to 2 times mol, and the mixture is heated and stirred. Examples of butyl bromide (chloride), pentyl bromide (chloride), hexyl bromide (chloride), heptyl bromide (chloride), octyl bromide (chloride), nonyl bromide (chloride), decyl bromide (chloride), 5-bromo ( Chloro) valeronitrile, 7-bromo (chloro) pentenenitrile, 3-bromo (chloro) -2-methyl-1-propanol, 6-bromo (chloro) hexanol and the like. Examples of alkyl tosylates include tosyl. Butyl acid, pentyl tosylate, Hexyl Le acids, ethoxyethyl tosylate, tosylate propoxyethyl, do not the like tosylate butoxyethyl can be mentioned as being limited thereto.

The alkali used in the above reaction is added for the purpose of neutralizing the hydrogen halide generated by the reaction of alkyl halides or the tosylic acid generated by the reaction of alkyl tosylate to neutralize the acids. Specific examples thereof include, but are not limited to, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine and the like.

After completion of the reaction, the reaction product can be taken out of the reaction solution by adding water to the reaction solution, further adding salt, etc. to salt out, crystallizing the dye of the present invention, and filtering.

The alkali developing negative coloring photosensitive composition of the present invention is a composition containing a binder polymer, a photopolymerizable monomer or oligomer, a thermosetting agent, a photoinitiator, a dye, and an organic solvent, Alternatively, a dye represented by the general formula (I) is partially used.

The binder polymer used in the present invention is used for the purpose of imparting the property (coating property) that the colored photosensitive composition of the present invention can be uniformly applied to a substrate. As a property required for the binder polymer, it is further necessary to be soluble in a developing solution used in a developing process at the time of manufacturing a color filter, and examples thereof include an alkaline aqueous solution-soluble resin and a water-soluble resin.

The alkaline aqueous solution-soluble resin used in the present invention is preferably a polymer containing a carboxyl group, particularly an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “other unsaturated monomers”) (hereinafter simply referred to as “carboxyl group-containing copolymer”). Is preferred). These carboxyl group-containing ethylenically unsaturated monomers and other unsaturated monomers can be used alone or in admixture of two or more.

The water-soluble resin in the present invention is preferably an acrylic, methacrylic, polyvinyl alcohol, polyvinylpyrrolidone, acryloylmorpholine resin or the like. Specific examples of the acrylic resin include polymers such as acrylic acid, sodium acrylate and acrylamide, and copolymers thereof. Examples of the methacrylic resin include polymers and copolymers such as methacrylic acid, sodium methacrylate, and 2-hydroxymethacrylic acid.

In this invention, a binder polymer can be used individually or in mixture of 2 or more types. The usage-amount of the binder polymer in this invention is 5-80 weight part normally with respect to 100 weight part of total solid of a negative coloring photosensitive composition, Preferably it is 10-60 weight part. In this case, if the amount of the binder polymer used is less than 10 parts by weight, for example, alkali developability may be deteriorated, or background contamination or film residue may occur in a region other than a portion where pixels are formed. If the amount exceeds part by weight, the dye concentration is relatively lowered, so that it may be difficult to achieve the target color density in the thin film.

As a weight average molecular weight (Mw) of the copolymer of a binder polymer, it is 2000-400000 normally, Preferably it is 3000-200000. When the weight average molecular weight is 2,000 or less, and when the number average molecular weight is 400,000 or more, the sensitivity and developability deteriorate.

Examples of the photopolymerizable monomer or oligomer used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol. Di (meth) acrylate, triethyleneglycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy (Meth) acrylate, bisphenol -F type epoxy di (meth) acrylate, bisphenol - fluorene epoxy di (meth) acrylate.

These may be used alone or in combination of two or more. The total amount of the photopolymerizable monomer or oligomer is 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total solid content of the negative coloring photosensitive composition.

Examples of the thermosetting agent used in the present invention include epoxy resins and melamine resins. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ether, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane Type epoxy resin, dihydroxybenzene type epoxy resin and the like, and examples of the melamine resin include, but are not limited to, polymethylol melamine resin and polymethylol benzoguanamine resin. The total amount of the thermosetting agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the negative coloring photosensitive composition. A thermosetting agent may be used independently and may be used in combination of 2 or more types.

The photoinitiator used in the present invention is preferably one having sensitivity to ultraviolet rays emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source. The total amount of the photopolymerization initiator is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total solid content of the negative coloring photosensitive composition.

  Examples of the photoinitiator include benzyl, benzoin methyl ether, benzoin butyl methyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, benzoylbenzoic acid ester compound, 4-benzoyl -4'-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, dimethyl Aminobenzoic acid isoamide ester, 1- (4-dodecylphenyl) -2-hydroxy-methyl Lopan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, methylbenzoyl formate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 5′-tetraphenylbisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) bisimidazole, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-to Azine, 2,4-bis (tribromomethyl) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3 5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- ( 4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-O-acetate and the like. In addition, other photo radical initiators and photo acid generators can be mixed and used as necessary.

The negative coloring photosensitive composition of the present invention may be used alone or in combination with other dyes for the coloring photosensitive composition of the present invention. As other dyes to be used in combination, a dye soluble in an organic solvent is selected and used. These dyes include acid dyes, basic dyes, direct dyes, vat dyes, reactive dyes, disperse dyes and the like.

Further, for example, a combination of a sulfone group of an acid dye, a direct dye or a reactive dye and a salt of an alkylamine can be used. Examples of alkylamines include, but are not limited to, n-propylamine, 2-ethylhexylpropylamine, 2-ethylhexyloxypropylamine, dibutylamine and the like.

A dye having a sulfamoyl group obtained by directly reacting the amines with a sulfone group is also very useful as a combined pigment. These dyes are composed of a part of pigment, acid dye, basic dye, direct dye, vat dye, reactive dye, disperse dye, etc. with chlorosulfonic acid or thionyl chloride acting on the dye skeleton to form —SO ₂ Cl group. It is then obtained by condensing this —SO ₂ Cl group and the amines by known methods. The pigment | dye which improved the solvent solubility by the above methods can be used for the negative coloring photosensitive composition of this invention.

The other dye used in combination is used in the range of 0 to 60% by weight, more preferably 0 to 40% by weight in the total dye, based on the coloring photosensitive composition coloring matter of the present invention.

The organic solvent used in the present invention preferably dissolves a binder polymer, a photopolymerizable monomer or oligomer, a photopolymerization initiator, and a dye, which are components of the negative coloring photosensitive composition. Examples of usable organic solvents include benzenes such as benzene, toluene and xylene, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol Propylene glycol monoalkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propionic acid such as methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate Esters, lactate esters such as methyl lactate, ethyl lactate, butyl lactate, etc. Diethylene glycols such as ethylene glycol monomethyl ether and diethylene glycol monoethyl ether, acetates such as methyl acetate, ethyl acetate, and butyl acetate, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone And ketones.

You may use these individually or in combination of 2 or more types. Moreover, the addition amount of the organic solvent is 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the total solid content of the negative coloring photosensitive composition.

The negative colored photosensitive composition of the present invention is prepared by stirring and dissolving the binder polymer, photopolymerizable monomer or oligomer, photopolymerization initiator, dye, polymerization inhibitor, organic solvent with a dissolver, homomixer, or the like. Manufactured.

The negative coloring photosensitive composition of the present invention may further contain various additives as necessary, for example, fillers, surfactants, thermal polymerization inhibitors, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors. An agent can be blended. To be shipped as a product, it is manufactured by microfiltration with a filter to remove foreign substances.

In the color filter of the present invention, at least one color pixel is composed of a cured film of the above-described negative coloring photosensitive composition. For example, in a color filter composed of three colors, one or two color pixels may be the above-described colored photosensitive composition, and the remaining color pixels may be a pigment-dispersed colored photosensitive composition containing a pigment. In addition, any of the three colors of pixels may be the above-described negative coloring photosensitive composition.

A liquid crystal display element having a color filter composed of a colored cured film pixel of the negative coloring photosensitive composition of the present invention includes a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, the color filter of the present invention, and a polarized light. Films are manufactured in this order, and a solid-state imaging device is manufactured by providing the color filter layer of the present invention on a silicon wafer with transfer electrodes and photodiodes, and then stacking microlenses. Is done.

  Hereinafter, the present invention will be described in more detail with reference to examples. In Examples, “part” means “part by weight” and “%” means “% by weight”.

Reference example 1
To a 300 ml four-necked flask, 160 parts by weight of dimethylformamide was added, then 20.5 parts by weight of CI Acid Blue 90, 9.8 parts by weight of 1-bromo-n-butane, and 5.0 parts by weight of potassium carbonate were added. While stirring, the mixture was heated to 120 ° C. and kept at the same temperature for 2 hours. Then it was cooled to room temperature. The reaction solution was slowly added to a beaker containing 600 parts by weight of pure water while stirring, and then 30 parts by weight of hydrochloric acid was added to precipitate the precipitated crystals, followed by filtration and washing with water. 18.6 parts by weight of the dye for the composition was obtained.

Reference example 2
To a 300 ml four-necked flask, 160 parts by weight of dimethylformamide was added, then 20.5 parts by weight of CI Acid Blue 90, 10.9 parts by weight of 1-bromo-n-pentane, and 5.0 parts by weight of potassium carbonate were added. While stirring, the mixture was heated to 120 ° C. and kept at the same temperature for 2 hours. Then it was cooled to room temperature. The reaction solution was slowly added to a beaker containing 600 parts by weight of pure water while stirring, and then 30 parts by weight of hydrochloric acid was added to precipitate the precipitated crystals, followed by filtration and washing with water. 19.9 parts by weight of the dye for the composition was obtained.

Reference example 3
To a 100 ml four-necked flask was added 40 parts by weight of dimethylacetamide, and then 20.5 parts by weight of CI Acid Blue 90, 11.6 parts by weight of 1-bromo-n-octane, and 4.1 parts by weight of potassium carbonate were added. While stirring, the mixture was heated to 90 ° C. and kept at the same temperature for 8 hours. Then it was cooled to room temperature. The reaction solution was slowly added to a beaker containing 250 parts by weight of pure water while stirring, and then 7 parts by weight of hydrochloric acid was added to precipitate the precipitated crystals, followed by filtration and washing with water. 28.0 parts by weight of the dye for the composition was obtained.

実施例４
バインダーポリマーとしてメタクリル酸１８重量％、ベンジルメタクリレート８２重量％からなる樹脂０．１７ｇ、光重合性モノマーとしてカヤラッドＤＰＨＡ（日本化薬製）０．１７ｇ、光開始剤にイルガキュアー３６９（チバ・スペシャリティ・ケミカルズ製）０．１ｇ、熱硬化剤にＭＸ−０４２（三和ケミカル製）０．１ｇ、染料に参考例１で示される着色感光性組成物用色素０．１ｇ、乳酸エチル３ｇ、重合禁止剤にＮ−ニトロソフェニルヒドロキシルアミンアンモニウム塩（和光純薬製）０．０００５ｇを混合し、本発明で使用するネガ型感光性組成物を得た。

Example 4
0.17 g of a resin consisting of 18% by weight of methacrylic acid as a binder polymer and 82% by weight of benzyl methacrylate, 0.17 g of Kayrad DPHA (manufactured by Nippon Kayaku) as a photopolymerizable monomer, Irgacure 369 (Ciba Specialty) as a photoinitiator (Manufactured by Chemicals) 0.1 g, thermosetting agent MX-042 (manufactured by Sanwa Chemical) 0.1 g, dyestuff for coloring photosensitive composition 0.1 g shown in Reference Example 1, ethyl lactate 3 g, polymerization inhibitor Was mixed with 0.0005 g of N-nitrosophenylhydroxylamine ammonium salt (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a negative photosensitive composition used in the present invention.

Next, the negative photosensitive composition obtained above is applied onto a substrate, and after being cured by exposure, the exposed area is further cured by heating at 100 ° C., followed by development at 200 ° C. Got no blue filter.

In addition, the negative photosensitive composition obtained above was applied onto a substrate, and after curing by exposure, the exposed portion was further cured by heating at 100 ° C., developed with an alkaline aqueous solution, rinsed with water, and 200 A blue filter which was heated at ℃ and subjected to the development process was obtained.

Examples 5 and 6
In the same manner as in Example 4, after obtaining a negative photosensitive composition using the coloring photosensitive composition dyes obtained in Reference Examples 2 and 3, a blue filter was prepared in the same manner.

Comparative Example 1
In the same manner as in Example 4, after obtaining a negative photosensitive composition using CI Acid Blue 90 as the coloring photosensitive composition dye, a blue filter was prepared in the same manner.

Comparative Example 2
A salt of CI Acid Blue 90 and 2-ethylhexyloxypropylamine was synthesized by a known method, and this dye was used as a dye for the colored photosensitive composition to prepare a colored photosensitive composition in the same manner as in Example 4. After obtaining, a blue filter was prepared in the same manner.

The blue filters obtained in Examples 4 to 6 and Comparative Examples 1 and 2 were characterized by the following method, and the results are shown in Table 2.
Characteristic A: It was observed by an optical microscope whether or not the coloring photosensitive composition dye was completely dissolved in the blue filter.
Characteristic B: The color difference (ΔE) of the blue filter that was subjected to the development process relative to the blue filter that was not subjected to the development process was measured with a spectrophotometer UV-2200 (manufactured by Shimadzu Corporation).

(Table 2)
Table 2
Characteristic A Characteristic B
Example 4 Complete dissolution 1.8
Example 5 Complete dissolution 1.2
Example 6 Complete dissolution 0.8
Comparative Example 1 Incomplete dissolution ―――
Comparative Example 2 Complete dissolution 25.1

As is clear from the characteristic A in Table 2, C.I. Acid Blue 90 of Comparative Example 1 does not completely dissolve in the solvent, so that sufficient optical characteristics cannot be obtained. Further, as is clear from the characteristic B in Table 2, in the salt form, the color difference (ΔE) of the blue filter that has undergone the development process with respect to the blue filter that has not undergone the development process is as extremely large as 25.1, and the color is lost. I understand that. On the other hand, the coloring matter of the present invention has good solubility in a solvent and ΔE of characteristic B is very small, 0.8 to 1.8, and hardly loses color. Therefore, when the present invention is used, a good blue filter can be obtained even after the development process.

Claims (3)

Formula (I)

(In the formula, R ₁ represents a linear alkyl group having 4 to 10 carbon atoms , R ₂ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or an alkali metal.)
An alkali-developing negative coloring photosensitive composition containing a dye , a binder polymer, a photopolymerizable monomer or oligomer, a thermosetting agent, a photoinitiator, and an organic solvent . The liquid crystal display element which has a color filter created using the negative coloring photosensitive composition of Claim 1 . The solid-state image sensor which has a color filter produced using the negative coloring photosensitive composition of Claim 1 .